CN106053572B - A kind of preparation method of electrochemistry bisphenol-A sensor - Google Patents
A kind of preparation method of electrochemistry bisphenol-A sensor Download PDFInfo
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- CN106053572B CN106053572B CN201610521340.8A CN201610521340A CN106053572B CN 106053572 B CN106053572 B CN 106053572B CN 201610521340 A CN201610521340 A CN 201610521340A CN 106053572 B CN106053572 B CN 106053572B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
Abstract
The invention discloses a kind of preparation methods of electrochemistry bisphenol-A sensor.The method comprises the steps of firstly, preparing a kind of New Two Dimensional nano-electrode material Mn-TiO2/MoS2That is the two-dimensional nano composite material of additive Mn nano titania square In-situ reaction molybdenum disulfide, good biocompatibility and big specific surface area using the material, bisphenol-A antibody in load, when being detected, since additive Mn titanium dioxide can be with catalyzing hydrogen peroxide in-situ preparation O2, electrochemical signals are generated, recycle antibody in conjunction with the specific quantification of antigen to the influence of electron transport ability, so that current strength accordingly reduces, finally realize the building of the biosensor using unmarked electrochemical method detection bisphenol-A.
Description
Technical field
The present invention relates to a kind of preparation methods of electrochemistry bisphenol-A sensor.Belong to Nano-function thin films and biology
Sensor technical field.
Background technique
After environmental estrogens refer to that one kind enters body, synthesis, release, fortune with normal endocrine substance in interfering bodies
The processes such as defeated, combination, metabolism, activate or inhibit the function of endocrine system, maintain organism stability and regulation to make to destroy
Compound, environmental estrogens are many kinds of, including artificial-synthetic compound and natural plant estrogen, are distributed widely in certainly
In right boundary.Bisphenol-A is a type bisphenols synthetic estrogen.
Currently, the method for detection bisphenol-A mainly has chromatography, mass spectrography etc..Such method instrument is valuable, complicated for operation,
Laboratory personnel just can be carried out detection after needing professional training.Therefore, research and development are at low cost, detection is fast, high sensitivity, high specificity
Bisphenol-A sensor is of great significance.
Electrochemica biological sensor due to its high sensitivity, specificity it is good, easy to operate the advantages that be widely used in facing
The fields such as bed diagnosis, Pharmaceutical Analysis, environmental monitoring.More, key is wherein studied with unmarked electrochemical immunosensor especially
Technology be to improve modified electrode to the fixed amount of antibody and to the signal response speed and size of test bottom liquid.Titanium dioxide is
A kind of photocatalyst material being most widely used, simultaneously because good biocompatibility, is also commonly used as electrode matrix material.By
More high miller index surfaces can be exposed in sheet-like titanium dioxide nanomaterial, there is higher catalytic activity, titanium dioxide is received
Rice piece has application prospect preferably than nanoparticle, and the research of titanium dioxide nanoplate is also concerned.But dioxy
The sensitivity that change titanium poorly conductive also limits the electrochemical sensor constructed by single titanium dioxide nano material is not generally high,
It is unfavorable for practical application.Modification or compound special nano material, on the one hand increase electrode ratio on semiconductor nano material
Surface area enhances electrodes conduct ability, and on the other hand the two can produce concerted catalysis effect, and bigger enhancing is to hydrogen peroxide
Solution H2O2Catalytic response speed and current responsing signal size, greatly improve detection sensitivity.Therefore, it designs, prepare height
Effect, stable titanium dioxide nanoplate and its modifier are the key technologies for preparing electrochemical sensor.
Molybdenum disulfide (chemical formula MoS2) nano material, there is two-dimensional layered structure, be most widely used solid profit
One of lubrication prescription.Its sheet two-dimension nano materials after removing, is the semiconductor nano material haveing excellent performance, in addition to big ratio
Surface area, can be used as the carrier of catalyst and biological antibody, improve load capacity, while also have as co-catalyst excellent
Electron transmission performance.
Currently, most of synthesizing mean is all after being separately synthesized, then catalyst and carrier progress is compound, process is numerous
Trivial, yield is not high.Therefore, before being had a wide range of applications for In-situ reaction preparation with the photosensitizer of excellent photoelectrochemical behaviour
Scape and important scientific meaning.
Summary of the invention
The purpose of the present invention is to provide it is a kind of prepare simple, high sensitivity, detection quickly, the electrochemistry of high specificity it is double
The preparation method of phenol A sensor, prepared sensor can be used for quick, the Sensitive Detection of bisphenol-A.Based on this purpose, this hair
It is bright to be prepared for a kind of New Two Dimensional nano-electrode material Mn-TiO first2/MoS2, i.e. additive Mn nano titania square is in situ
The two-dimensional nano composite material of composite molybdenum disulfide, good biocompatibility and big specific surface area using the material are born
Bisphenol-A antibody in load, when being detected, since additive Mn titanium dioxide can be with catalyzing hydrogen peroxide in-situ preparation O2, generate
Electrochemical signals recycle antibody in conjunction with the specific quantification of antigen to the influence of electron transport ability, so that current strength
It is corresponding to reduce, finally realize the building of the biosensor using unmarked electrochemical method detection bisphenol-A.
The technical solution adopted by the invention is as follows:
1. a kind of preparation method of electrochemistry bisphenol-A sensor, it is characterised in that the electrochemistry bisphenol-A sensor
By working electrode, Mn-TiO2/MoS2, bisphenol-A antibody, bovine serum albumin(BSA) composition, the Mn-TiO2/MoS2For additive Mn
The two-dimensional nano composite material of nano titania square In-situ reaction molybdenum disulfide；
It is characterized in that, the preparation method includes following preparation step:
A. Mn-TiO is prepared2/MoS2；
B. electrochemistry bisphenol-A sensor is prepared；
Wherein, step a prepares Mn-TiO2/MoS2Specific steps are as follows:
(1) 0.6 g molybdenum disulfide powder and 0.2 ~ 2.0 mmol manganese salt is taken to be added to 3 ~ 10 mL n-BuLis jointly molten
In liquid, at nitrogen protection and 30 ~ 60 DEG C, stir 12 ~ 48 hours, the solution after being reacted；
(2) using the solution after reaction in nonpolar solvent washing step (1), water-bath is then carried out at 30 ~ 60 DEG C
Ultrasonic treatment, after handle, recycle nonpolar solvent carrying out washing treatment after solution, be dried in vacuo, obtain two sulphur of manganese intercalation
Change molybdenum nano material；
(3) the molybdenum disulfide nano material of manganese intercalation made from 10 ~ 500 mg steps (2) is taken to be added to 5 mL metatitanic acids four
In butyl ester, after stirring 1 hour, it is slowly added to 0.5 ~ 0.8 mL hydrofluoric acid while stirring, is then reacting at 160 ~ 180 DEG C
It is reacted 18 ~ 20 hours in kettle；
(4) by step (3) resulting reaction product, with ultrapure water and dehydrated alcohol centrifuge washing three times after, it is true at 50 DEG C
Sky is dry, obtains Mn-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The manganese salt is selected from one of following: manganese sulfate, manganese chloride, manganese nitrate, organo-manganese compound；
The nonpolar solvent is selected from one of following: hexane, hexamethylene, carbon tetrachloride, benzene, toluene；
The water bath sonicator processing, processing time are 1 hour；
The specific steps of step b preparation electrochemistry bisphenol-A sensor are as follows:
(1) using ITO electro-conductive glass as working electrode, in the Mn-TiO of 8 ~ 12 μ L of electrode surface drop coating2/MoS2Colloidal sol, room
It is dried under temperature；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 8 ~ 12 μ L of electrode surface drop coating
The bisphenol-A antibody-solutions of 10 μ g/mL are saved in 4 DEG C of refrigerators and are dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 8 ~ 12 μ L concentration of electrode surface drop coating to be 100
The bovine serum albumin solution of μ g/mL is saved in 4 DEG C of refrigerators and is dried；
(4) electrode obtained in step (3) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, obtains electrification
Learn bisphenol-A sensor；
The Mn-TiO2/MoS2Colloidal sol is by the Mn-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultrapure waters, and
The hydrosol obtained after 30 min of ultrasound；
The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is 7.4.
2. the application of electrochemistry bisphenol-A sensor prepared by preparation method of the present invention, which is characterized in that packet
Include following applying step:
A. standard solution is prepared: preparing the bisphenol-A standard solution of one group of various concentration including blank standard specimen；
B. working electrode is modified: by electrochemistry bisphenol-A sensor prepared by preparation method as described in claim 1
For working electrode, the bisphenol-A standard solution for the various concentration prepared in step a is distinguished into drop coating to working electrode surface, 4 DEG C
It is saved in refrigerator；
C. working curve is drawn: saturated calomel electrode electrode is used as to reference electrode, platinum electrode as to electrode, with
The working electrode that step b has been modified forms three-electrode system, connects electrochemical workstation, and 15 are successively added in a cell
The H of 5 mol/L of mL PBS and 20 μ L2O2；By the working electrode of chronoamperometry detection assembling to H2O2Response；Blank
The response current of standard specimen is denoted asI 0, the response current of the bisphenol-A standard solution containing various concentration is denoted asI i, response current reduction
Difference be ΔI = I 0-I i, ΔIWith the mass concentration of bisphenol-A standard solutionCBetween it is linear, draw ΔI?CWork
Curve；
D. the detection of bisphenol-A: the bisphenol-A standard solution in step a is replaced with sample to be tested, according to the side in step b and c
Method is detected, the difference DELTA that electrical signal intensity reduces according to responseIAnd working curve, obtain containing for bisphenol-A in sample to be tested
Amount.
Beneficial achievement of the invention
(1) electrochemistry bisphenol-A sensor of the present invention preparation is simple, easy to operate, realize to sample it is quick,
Sensitive, highly selective detection, and it is at low cost, it can be applied to portable inspectiont, there is market development prospect；
(2) present invention is prepared for New Two Dimensional nano-electrode material Mn-TiO using the method for In-situ reaction for the first time2/MoS2,
This method is mainly there are three advantage: first is that, sufficiently and titanium dioxide due to growth in situ of the manganese on nano titania square
The contact of titanium nano square is acted on using the metal surface plasma body of manganese, effectively increases semiconductor substrate electron transmission ability
And catalytic activity, although solving, titanium dioxide nanoplate specific surface area is bigger and mesoporous characteristic is suitable for electrochemical-based material
Material, but the technical problem that electro-chemical activity is not high and current signal is unstable；Second is that due to molybdenum disulfide sheet two-dimensional nano
The load characteristic and nano titania square of material on it fully dispersed, greatly increase electron transmission ability, solve
Determined titanium dioxide nanoplate poorly conductive and current responsing signal it is weak and be unfavorable for the technical issues of preparing electrochemical sensor；
Third is that since manganese ion is in this process not only as intercalation material but also as reaction dopant material, finally using In-situ reaction
Method realizes one pot of preparation of the composite material, not only saves time, material loss, and make the additive Mn of preparation
Nano titania square can preferably be evenly spread to above molybdenum disulfide sheet two-dimension nano materials.Therefore, the material
Effective preparation, have important scientific meaning and application value；
(3) present invention is for the first time by Mn-TiO2/MoS2Applied in the preparation of electrochemica biological sensor, electricity is significantly improved
The strength and stability for flowing signal, substantially increases the detection sensitivity of electrochemical sensor, so that electrochemica biological sensor
Realize application in actual operation；The application of the material is also associated biomolecule sensor, such as optical electro-chemistry sensor, electricity
It causes chemiluminescence sensor etc. to provide Technical Reference, there is extensive potential use value.
Specific embodiment
1 Mn-TiO of embodiment2/MoS2Preparation
(1) 0.6 g molybdenum disulfide powder and 0.2 mmol manganese salt is taken to be added in 3mL n-butyllithium solution jointly, in nitrogen
At gas shielded and 60 DEG C, stir 12 hours, the solution after being reacted；
(2) using the solution after reaction in nonpolar solvent washing step (1), water bath sonicator is then carried out at 60 DEG C
Processing, after handle, recycle nonpolar solvent carrying out washing treatment after solution, be dried in vacuo, obtain the molybdenum disulfide of manganese intercalation
Nano material；
(3) the molybdenum disulfide nano material of manganese intercalation made from 500 mg steps (2) is taken to be added to 5 mL butyl titanates
In, after stirring 1 hour, it is slowly added to 0.5 mL hydrofluoric acid while stirring, then reacts in a kettle 18 hours at 160 DEG C；
(4) by step (3) resulting reaction product, with ultrapure water and dehydrated alcohol centrifuge washing three times after, it is true at 50 DEG C
Sky is dry, obtains Mn-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The manganese salt is manganese sulfate；
The nonpolar solvent is hexane；
The water bath sonicator processing, processing time are 1 hour.
2 Mn-TiO of embodiment2/MoS2Preparation
(1) 0.6 g molybdenum disulfide powder and 1.0 mmol manganese salts is taken to be added in 5 mL n-butyllithium solutions jointly, in nitrogen
At gas shielded and 30 DEG C, stir 24 hours, the solution after being reacted；
(2) using the solution after reaction in nonpolar solvent washing step (1), water bath sonicator is then carried out at 30 DEG C
Processing, after handle, recycle nonpolar solvent carrying out washing treatment after solution, be dried in vacuo, obtain the molybdenum disulfide of manganese intercalation
Nano material；
(3) the molybdenum disulfide nano material of manganese intercalation made from 200 mg steps (2) is taken to be added to 5 mL butyl titanates
In, after stirring 1 hour, it is slowly added to 0.6 mL hydrofluoric acid while stirring, then reacts in a kettle 20 hours at 180 DEG C；
(4) by step (3) resulting reaction product, with ultrapure water and dehydrated alcohol centrifuge washing three times after, it is true at 50 DEG C
Sky is dry, obtains Mn-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The manganese salt is manganese chloride；
The nonpolar solvent is carbon tetrachloride；
The water bath sonicator processing, processing time are 1 hour.
The preparation method of 3 electrochemistry bisphenol-A sensor of embodiment
(1) using ITO electro-conductive glass as working electrode, in the Mn-TiO of 8 μ L of electrode surface drop coating2/MoS2Colloidal sol, at room temperature
It dries；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 8 μ L of electrode surface drop coating, 10 μ
The bisphenol-A antibody-solutions of g/mL are saved in 4 DEG C of refrigerators and are dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 8 μ L concentration of electrode surface drop coating to be 100 μ
The bovine serum albumin solution of g/mL is saved in 4 DEG C of refrigerators and is dried；
(4) electrode obtained in step (3) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, obtains electrification
Learn bisphenol-A sensor；
The Mn-TiO2/MoS2Colloidal sol is by the Mn-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultrapure waters, and
The hydrosol obtained after 30 min of ultrasound；
The PBS is the phosphate buffer solution of 10mmol/L, and the pH value of the phosphate buffer solution is 7.4.
The preparation method of 4 electrochemistry bisphenol-A sensor of embodiment
(1) using ITO electro-conductive glass as working electrode, in the Mn-TiO of 10 μ L of electrode surface drop coating2/MoS2Colloidal sol, room temperature
Under dry；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 10 μ L 10 of electrode surface drop coating
The bisphenol-A antibody-solutions of μ g/mL are saved in 4 DEG C of refrigerators and are dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 10 μ L concentration of electrode surface drop coating to be 100 μ
The bovine serum albumin solution of g/mL is saved in 4 DEG C of refrigerators and is dried；
(4) electrode obtained in step (3) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, obtains electrification
Learn bisphenol-A sensor；
The Mn-TiO2/MoS2Colloidal sol is by the Mn-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultrapure waters, and
The hydrosol obtained after 30 min of ultrasound；
The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is 7.4.
The preparation method of 5 electrochemistry bisphenol-A sensor of embodiment
(1) using ITO electro-conductive glass as working electrode, in the Mn-TiO of 12 μ L of electrode surface drop coating2/MoS2Colloidal sol, room temperature
Under dry；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 12 μ L 10 of electrode surface drop coating
The bisphenol-A antibody-solutions of μ g/mL are saved in 4 DEG C of refrigerators and are dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 12 μ L concentration of electrode surface drop coating to be 100 μ
The bovine serum albumin solution of g/mL is saved in 4 DEG C of refrigerators and is dried；
(4) electrode obtained in step (3) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, obtains electrification
Learn bisphenol-A sensor；
The Mn-TiO2/g-C3N4Colloidal sol is by the Mn-TiO of 50 mg2/g-C3N4Powder is dissolved in 10 mL ultrapure waters
In, and the hydrosol obtained after 30 min of ultrasound；
The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is 7.4.
The electrochemistry bisphenol-A sensor of 6 embodiment 1 ~ 5 of embodiment preparation, applied to the detection of bisphenol-A, steps are as follows:
(1) standard solution is prepared: preparing the bisphenol-A standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: by electrochemistry bisphenol-A sensor prepared by preparation method as described in claim 1
For working electrode, the bisphenol-A standard solution for the various concentration prepared in step (1) is distinguished into drop coating to working electrode surface, 4
It is saved in DEG C refrigerator；
(3) working curve is drawn: saturated calomel electrode electrode is used as to reference electrode, platinum electrode as to electrode, with
The working electrode that step b has been modified forms three-electrode system, connects electrochemical workstation, and 15 are successively added in a cell
The H of 5 mol/L of mL PBS and 20 μ L2O2；By the working electrode of chronoamperometry detection assembling to H2O2Response；Blank
The response current of standard specimen is denoted asI 0, the response current of the bisphenol-A standard solution containing various concentration is denoted asI i, response current reduction
Difference be ΔI = I 0-I i, ΔIWith the mass concentration of bisphenol-A standard solutionCBetween it is linear, draw ΔI?CWork
Curve；The linear detection range of bisphenol-A are as follows: 0.009 ~ 200 ng/mL, detection limit are as follows: 3.0 pg/mL；
(4) detection of bisphenol-A: replacing the bisphenol-A standard solution in step (1) with sample to be tested, according to step (2) and
(3) method in is detected, the difference DELTA that electrical signal intensity reduces according to responseIAnd working curve, it obtains in sample to be tested
The content of bisphenol-A.
Claims (1)
1. a kind of preparation method of electrochemistry bisphenol-A sensor, it is characterised in that the electrochemistry bisphenol-A sensor is by working
Electrode, Mn-TiO2/MoS2, bisphenol-A antibody, bovine serum albumin(BSA) composition, the Mn-TiO2/MoS2For additive Mn titanium dioxide
The two-dimensional nano composite material of titanium nano square In-situ reaction molybdenum disulfide；
The Mn-TiO2/MoS2Specific preparation step are as follows: take 0.6 g molybdenum disulfide powder and 0.2 ~ 2.0 mmol manganese salt
It is added in 3 ~ 10 mL n-butyllithium solutions jointly, at nitrogen protection and 30 ~ 60 DEG C, stirs 12 ~ 48 hours, obtain
Solution after reaction；Using the solution after nonpolar solvent washing reaction, then carried out at water bath sonicator at 30 ~ 60 DEG C
Reason, after handle, solution after recycling nonpolar solvent carrying out washing treatment is dried in vacuo, the molybdenum disulfide for obtaining manganese intercalation receives
Rice material；It takes the molybdenum disulfide nano material of manganese intercalation made from 10 ~ 500 mg to be added in 5 mL butyl titanates, stirs
After 1 hour, it is slowly added to 0.5 ~ 0.8 mL hydrofluoric acid while stirring, then react 18 at 160 ~ 180 DEG C in a kettle ~
20 hours, resulting reaction product, with ultrapure water and dehydrated alcohol centrifuge washing three times after, be dried in vacuo, obtain at 50 DEG C
Mn-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The manganese salt is selected from one of following: manganese sulfate, manganese chloride, manganese nitrate, organo-manganese compound；
The nonpolar solvent is selected from one of following: hexane, hexamethylene, carbon tetrachloride, benzene, toluene；
The water bath sonicator processing, processing time are 1 hour；
The specific preparation step of the electrochemistry bisphenol-A sensor are as follows:
(1) using ITO electro-conductive glass as working electrode, in the Mn-TiO of 8 ~ 12 μ L of electrode surface drop coating2/MoS2Colloidal sol, at room temperature
It dries；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 8 ~ 12 μ L of electrode surface drop coating, 10 μ
The bisphenol-A antibody-solutions of g/mL are saved in 4 DEG C of refrigerators and are dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 8 ~ 12 μ L concentration of electrode surface drop coating to be 100 μ g/
The bovine serum albumin solution of mL is saved in 4 DEG C of refrigerators and is dried；
(4) electrode obtained in step (3) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, it is double obtains electrochemistry
Phenol A sensor；
The Mn-TiO2/MoS2Colloidal sol is by the Mn-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultrapure waters, and ultrasound
The hydrosol obtained after 30 min；
The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is 7.4.
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